Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
  • B29C41/02—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
  • B29C41/14—Dipping a core
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/02—Direct processing of dispersions, e.g. latex, to articles
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
  • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
  • C08J3/05—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media from solid polymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
  • B29C41/003—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor characterised by the choice of material
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/42—Nitriles
  • C08F220/44—Acrylonitrile
  • C08F220/46—Acrylonitrile with carboxylic acids, sulfonic acids or salts thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L13/00—Compositions of rubbers containing carboxyl groups
  • C08L13/02—Latex
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
  • C08L9/02—Copolymers with acrylonitrile
  • C08L9/04—Latex
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
  • C09D133/18—Homopolymers or copolymers of nitriles
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2007/00—Use of natural rubber as moulding material
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2009/00—Use of rubber derived from conjugated dienes, as moulding material
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
  • B29K2105/0058—Liquid or visquous
  • B29K2105/0064—Latex, emulsion or dispersion
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
  • B29L2031/00—Other particular articles
  • B29L2031/48—Wearing apparel
  • B29L2031/4842—Outerwear
  • B29L2031/4864—Gloves
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2313/00—Characterised by the use of rubbers containing carboxyl groups
  • C08J2313/02—Latex
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
  • C08K5/098—Metal salts of carboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/10—Esters; Ether-esters
  • C08K5/101—Esters; Ether-esters of monocarboxylic acids
  • C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols

Definitions

• the present invention relates to a latex composition for dip molding, and more particularly, to the latex composition for dip molding, a manufacturing method thereof, and a molded article manufactured therefrom.
• Latex molded products such as disposable rubber gloves
• natural rubber latex was dip-molded to make disposable gloves, but some users had problems with protein allergies such as pain or rash. Due to this problem, disposable gloves made by dip molding of nitrile latex instead of natural rubber latex have recently been in the spotlight.
• the problem to be solved in the present invention is, in order to solve the problems mentioned in the technology behind the background of the present invention, the synergy time is increased during dip molding by using the latex composition for dip molding to improve stability, from which It is to maintain the physical properties of dip-molded products such as manufactured gloves at the same or higher level.
• the present invention when preparing a carboxylic acid-modified nitrile-based copolymer latex composition, by including a cholate-based emulsifier, agglomeration of latex particles in the latex composition is eliminated to improve dispersibility, thereby improving the stability of the latex particles.
• the synergy time is ultimately increased during dip molding to improve stability, and at the same time, the tensile strength of dip molded products such as gloves manufactured therefrom is improved, and the latex composition for dip molding, which improves the fit by lowering the modulus. It is an object of the present invention to provide a manufacturing method and a dip molded article molded therefrom.
• a carboxylic acid-modified nitrile-based copolymer latex and a cholate-based emulsifier are included, and the cholate-based emulsifier is 100 parts by weight of the solid content of the carboxylic acid-modified nitrile-based copolymer latex
• the cholate-based emulsifier is 100 parts by weight of the solid content of the carboxylic acid-modified nitrile-based copolymer latex
• it provides a latex composition for dip molding contained in an amount of 0.02 to 3 parts by weight.
• the present invention is to prepare a carboxylic acid-modified nitrile-based copolymer latex (S10); And a step (S20) of mixing the prepared carboxylic acid-modified nitrile-based copolymer latex with a cholate-based emulsifier, and the step (S20) includes a cholate-based emulsifier and 100 weight of the solid content of the carboxylic acid-modified nitrile-based copolymer latex. It provides a method for producing a latex composition for dip molding that is mixed in an amount of 0.02 to 3 parts by weight based on parts.
• the present invention provides a molded article comprising a layer derived from the latex composition for dip molding.
• the latex composition for dip molding according to the present invention uses a cholate-based emulsifier having a hydrophilic group and a solid steroid ring skeleton at the same time, thereby improving the dispersibility of the latex particles and improving the stability of the latex. Due to this increase in synergy time, when dip-molded articles such as gloves are manufactured using this, workability and tensile strength are excellent, and wearability is improved due to a decrease in modulus.
• the term'monomer-derived repeating unit' may refer to a component, structure, or substance itself derived from a monomer, and as a specific example, when the polymer is polymerized, the input monomer participates in the polymerization reaction to form a repeat within the polymer. It may mean a unit.
• the term'latex' may mean that a polymer or copolymer polymerized by polymerization exists in a dispersed form in water, and as a specific example, of a rubber polymer or a rubber copolymer polymerized by emulsion polymerization. It may mean that the particulates exist in a colloidal state and dispersed in water.
• the term'derived layer' may refer to a layer formed from a polymer or a copolymer, and as a specific example, when manufacturing a dip molded article, a polymer or a copolymer is attached, fixed, and/or polymerized on a dip mold to form a polymer or It may mean a layer formed from a copolymer.
• crosslinking agent-derived crosslinking portion' may refer to a component, structure, or substance itself originated from a compound, and performs a role of crosslinking within or between polymers formed by the action and reaction of the crosslinking agent composition. It may mean a cross linking part.
• alkyl' is a linear or branched saturated monovalent hydrocarbon of carbon atoms, such as methyl, ethyl, propyl, 2-propyl, n-butyl, iso-butyl, tert-butyl, pentyl, hexyl, dodecyl, etc. It may mean, and it may mean to include not only unsubstituted ones but also those substituted by a substituent.
• cycloalkyl refers to cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, cycloheptyl, cyclooctyl, decahydronaphthalenyl, adamantanyl, norbornyl (i.e.
• the term'aryl' may mean that one or more of the hydrogen atoms of the alkyl group defined above are substituted with an aryl group, such as phenyl, naphthalenyl, fluorenyl, etc., and not only unsubstituted ones but also substituents It may mean to include those substituted by.
• the term'(meth)acrylate' may mean that both acrylate and methacrylate are possible.
• the latex composition for dip molding according to the present invention may include a carboxylic acid nitrile-based copolymer latex and a cholate-based emulsifier.
• the carboxylic acid-modified nitrile-based copolymer included in the carboxylic acid-modified nitrile-based copolymer latex is a repeating unit derived from a conjugated diene-based monomer, an ethylenically unsaturated repeating unit derived from a nitrile-based monomer, and ethylenically unsaturated. It may contain a repeating unit derived from an acid monomer.
• the conjugated diene-based monomer forming the repeating unit derived from the conjugated diene-based monomer is 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3 -It may be one or more selected from the group consisting of butadiene, 1,3-pentadiene, and isoprene, and as a specific example, it may be 1,3-butadiene or isoprene, and a more specific example, it may be 1,3-butadiene.
• the content of the repeating unit derived from the conjugated diene-based monomer may be 40% to 89% by weight, 45% to 80% by weight, or 50% to 78% by weight based on the total content of the carboxylic acid-modified nitrile-based copolymer, Within this range, a dip-molded article molded from a dip-molding latex composition containing the carboxylic acid-modified nitrile-based copolymer is flexible, has excellent touch and fit, and has excellent oil resistance and tensile strength.
• the ethylenically unsaturated nitrile-based monomer forming the repeating unit derived from the ethylenically unsaturated nitrile-based monomer is acrylonitrile, methacrylonitrile, hummaronitrile, ⁇ -chloronitrile and ⁇ -It may be one or more selected from the group consisting of cyanoethyl acrylonitrile, and specific examples may be acrylonitrile and methacrylonitrile, and a more specific example may be acrylonitrile.
• the content of the repeating unit derived from the ethylenically unsaturated nitrile-based monomer may be 10% to 50% by weight, 15% to 45% by weight, or 20% to 40% by weight based on the total content of the carboxylic acid-modified nitrile-based copolymer. And, within this range, a dip-molded article molded from a dip-molding latex composition containing the carboxylic acid-modified nitrile-based copolymer is flexible, has excellent touch and fit, and has excellent oil resistance and tensile strength.
• the ethylenically unsaturated acid monomer forming the repeating unit derived from the ethylenically unsaturated acid monomer may be an ethylenically unsaturated monomer containing an acidic group such as a carboxyl group, a sulfonic acid group, and an acid anhydride group
• an acidic group such as a carboxyl group, a sulfonic acid group, and an acid anhydride group
• Specific examples include ethylenically unsaturated acid monomers such as acrylic acid, methacrylic acid, itaconic acid, maleic acid and fumaric acid; Polycarboxylic anhydrides such as maleic anhydride and citraconic anhydride; Ethylenically unsaturated sulfonic acid monomers such as styrene sulfonic acid; It may be one or more selected from the group consisting of ethylenically unsaturated polycarboxylic acid partial ester monomers such as monobuty
• the content of the repeating unit derived from the ethylenically unsaturated acid monomer may be 0.1% to 15% by weight, 0.5% to 9% by weight, or 1% to 8% by weight based on the total content of the carboxylic acid-modified nitrile-based copolymer, and , Within this range, a dip-molded article molded from a dip-molding latex composition containing the carboxylic acid-modified nitrile-based copolymer is flexible, has excellent fit, and has excellent resistance and tensile strength.
• the carboxylic acid-modified nitrile-based copolymer latex is an ethylenically unsaturated monomer in addition to a repeating unit derived from a conjugated diene-based monomer, a repeating unit derived from an ethylenically unsaturated nitrile-based monomer, and a repeating unit derived from an ethylenically unsaturated acid monomer.
• the derived repeating unit may be optionally further included.
• the ethylenically unsaturated monomer forming the repeating unit derived from the ethylenically unsaturated monomer is a vinyl aromatic monomer selected from the group consisting of styrene, aryl styrene, and vinyl naphthalene; Fluoroalkyl vinyl ethers such as fluoro ethyl vinyl ether; (Meth)acrylamide, N-methylol (meth)acrylamide, N,N-dimethylol (meth)acrylamide, N-methoxy methyl (meth)acrylamide, and N-propoxy methyl (meth)acrylamide Ethylenically unsaturated amide monomers selected from the group consisting of; Non-conjugated diene monomers such as vinyl pyridine, vinyl norbornene, dicyclopentadiene, and 1,4-hexadiene; Methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)
• the content of the repeating unit derived from the ethylenically unsaturated monomer may be within 20% by weight, 0.01 to 20% by weight, or 0.01 to 15% by weight based on the total content of the carboxylic acid-modified nitrile-based copolymer, and within this range, the carboxylic acid-modified
• a dip-molded product molded from a dip-molding latex composition containing a nitrile-based copolymer has an excellent touch and fit, and excellent tensile strength.
• the carboxylic acid-modified nitrile-based copolymer latex may have a glass transition temperature of -50 °C to -15 °C, -47 °C to -15 °C, or -45 °C to -20 °C, Within this range, while preventing the occurrence of cracks and deterioration of tensile properties such as tensile strength of a molded article dip-molded from the latex composition for dip molding containing the carboxylic acid-modified nitrile-based copolymer latex, there is an effect of excellent wearing comfort due to low stickiness. .
• the glass transition temperature may be measured using a differential scanning calorimetry.
• the average particle diameter of the carboxylic acid-modified nitrile-based copolymer particles in the carboxylic acid-modified nitrile-based copolymer latex is 50 nm to 500 nm, 80 nm to 300 nm, or 100 nm to 150 nm, and within this range, the viscosity of the carboxylic acid-modified nitrile-based copolymer latex is not increased, so that a carboxylic acid-modified nitrile-based copolymer latex can be prepared at a high concentration, and dip from the latex composition for dip molding comprising the same.
• the average particle diameter may be measured using a laser scattering analyzer (Nicomp).
• the cholate-based emulsifier is cholic acid, glycocholic acid, taurocholic acid, deoxycholic acid, kenodioxycholic acid, glycokenodioxycholic acid, taurokenodioxycholic acid, and lysocholic acid. It may be one or more selected from the group consisting of, or in the form of a salt thereof, cholate, glycocholate, taurocholate, deoxycholate, kenodioxycholate, glycokenodioxycholate, taurokenodioxycholate, and lysocholate. It may be one or more selected from the group consisting of. Meanwhile, the salt may be a monovalent salt of sodium or potassium.
• the cholate-based emulsifier contains a hydroxyl group and a carboxylate group, which are hydrophilic groups, and thus has good miscibility and dispersibility in water.
• the cholate-based emulsifier has a solid steroid ring structure having hydrophobicity, and this hydrophobic structure allows the cholate-based emulsifier to adhere well to the surface of the carboxylic acid-modified nitrile-based copolymer particles.
• the carboxylic acid-modified nitrile-based copolymer increases the ion repulsion between particles, thereby reducing agglomeration between particles, thereby improving the dispersibility of the particles and further improving the stability of the latex.
• the manufacturing time of the latex film is delayed during the manufacturing of the molded article, and as a result, the synergy time is prolonged because the coagulant and water can be contained for a longer time.
• the content of the cholate-based emulsifier may be included in an amount of 0.02 to 3 parts by weight, specifically 0.1 to 2.2 parts by weight, more specifically 0.1 parts by weight, based on 100 parts by weight of the solid content of the carboxylic acid-modified nitrile-based copolymer latex. It may be from parts to 1.5 parts by weight, and within this range, the synergy time of the dip molding latex composition increases to improve stability, and the dip-molded article manufactured using the dip molding latex composition has the tensile strength of the glove. Has an increasing effect.
• the cholate-based emulsifier by using the cholate-based emulsifier, precipitation and coagulation are suppressed in the latex, and defects that may occur due to adsorption of coagulation or the like to the molded product can be suppressed. Through this, ultimately, the properties of the molded product are generally improved.
• the cholate-based emulsifier included in the dip molding latex composition is not a component derived from the production of the carboxylic acid-modified nitrile-based copolymer, but is prepared when the dip molding latex composition is prepared. It may be an emulsifier derived from additional addition and mixing to the carboxylic acid-modified nitrile-based copolymer, and may be different from the emulsifier added when preparing the carboxylic acid-modified nitrile-based copolymer.
• the latex composition for dip molding may further include additives such as a vulcanizing agent, an ionic crosslinking agent, a pigment, a vulcanization catalyst, a filler, and a pH adjusting agent, if necessary.
• additives such as a vulcanizing agent, an ionic crosslinking agent, a pigment, a vulcanization catalyst, a filler, and a pH adjusting agent, if necessary.
• the latex composition for dip molding for example, has a solid content (concentration) of 5% to 40% by weight, 8% to 35% by weight, or 10% to 33% by weight It may be, and within this range, the efficiency of the latex transport is excellent, and there is an effect of excellent storage stability by preventing an increase in the viscosity of the latex.
• the latex composition for dip molding may have a pH of 8 to 12, 9 to 11, or 9.3 to 11, and has excellent processability and productivity when manufacturing a dip-molded product within this range.
• the pH of the latex composition for dip molding may be adjusted by the introduction of the aforementioned pH adjusting agent.
• the pH adjusting agent may be, for example, an aqueous potassium hydroxide solution having a concentration of 1% to 5% by weight, or aqueous ammonia having a concentration of 1% to 5% by weight.
• the manufacturing method of the latex composition for dip molding according to the present invention comprises the steps of preparing a carboxylic acid-modified nitrile-based copolymer latex (S10); And mixing the prepared carboxylic acid-modified nitrile-based copolymer latex and a cholate-based emulsifier (S20).
• the method for preparing the latex composition for dip molding according to the present invention comprises a carboxylate-modified nitrile-based copolymer by polymerizing a monomer mixture containing a conjugated diene-based monomer, an ethylenically unsaturated nitrile-based monomer, and an ethylenically unsaturated acid monomer. Preparing a main acid-modified nitrile-based copolymer latex; And adding and mixing a cholate-based emulsifier to the prepared carboxylic acid-modified nitrile-based copolymer latex.
• the polymerization of the carboxylic acid-modified nitrile-based copolymer may be carried out by emulsion polymerization.
• the polymerization may be carried out by polymerization of the monomer mixture, and each monomer included in the monomer mixture may be added in the type and content of the aforementioned monomers, batch input, or continuously added.
• the monomer mixture may be simultaneously introduced into the polymerization reactor prior to polymerization, or a part of the monomer mixture may be first introduced into the polymerization reactor, and the remaining monomer mixture may be added after the polymerization is initiated.
• the monomer mixture is divided and added, when repeating units derived from monomers derived from each monomer in the carboxylic acid-modified nitrile-based copolymer are formed, the distribution of the monomers due to the difference in reaction rate for each monomer can be uniform. Accordingly, there is an effect of improving the balance between physical properties of a dip-molded article manufactured using a carboxylic acid-modified nitrile-based copolymer.
• the polymerization of the carboxylic acid-modified nitrile-based copolymer may be carried out in the presence of an emulsifier, a polymerization initiator, an activator, and a molecular weight modifier.
• the emulsifier is, for example, one or more selected from the group consisting of anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants.
• an alkylbenzene sulfonate, an aliphatic sulfonate, a higher alcohol sulfate ester salt, an ⁇ -olefin sulfonate salt, and an alkyl ether sulfate ester salt may be one or more anionic surfactants selected from the group consisting of.
• the emulsifier may be added in an amount of 0.3 parts by weight to 10 parts by weight, 0.8 parts by weight to 8 parts by weight, or 1.5 parts by weight to 8 parts by weight based on 100 parts by weight of the total monomer mixture, and polymerization stability is within this range. It is excellent, and there is an effect that it is easy to manufacture a molded product due to a small amount of foaming.
• the polymerization initiator may be, for example, an oxidation-reduction initiator and a thermal initiator.
• the oxidation-reduction initiator may include one or two or more selected from the group consisting of sodium disulfite, sodium sulfite, isoascorbic acid, and sodium formaldehyde sulfoxylate, and as a specific example, ascorbic acid may be used.
• the oxidation-reduction initiator may be 0.001 parts by weight to 5.0 parts by weight, 0.01 parts by weight to 4.0 parts by weight, or 0.05 to 3.0 parts by weight based on 100 parts by weight of the total monomer mixture, and maintain the polymerization rate at an appropriate level within this range. There is an effect that can be.
• the thermal initiator may include inorganic peroxides such as sodium persulfate, potassium persulfate, ammonium persulfate, potassium perphosphate and hydrogen peroxide; t-butyl peroxide, cumene hydroperoxide, p-mentanehydro peroxide, di-t-butyl peroxide, t-butylcumyl peroxide, acetyl peroxide, isobutyl peroxide, octanoyl peroxide, dibenzoyl peroxide Organic peroxides such as oxide, 3,5,5-trimethylhexanol peroxide and t-butyl peroxy isobutylate; Azobis isobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile, and azobis isobutyric acid (butyric acid) methyl.
• inorganic peroxides such as sodium persulfate
• the thermal initiator may be 0.01 parts by weight to 2.0 parts by weight, 0.02 parts by weight to 1.5 parts by weight, or 0.05 to 1.0 parts by weight based on 100 parts by weight of the total monomer mixture, and when used with the oxidation-reduction initiator within this range There is an effect of maintaining the polymerization rate at an appropriate level.
• the activator is sodium formaldehyde, sulfoxylate, sodium ethylenediamine terraacetate, ferrous sulfate, dextrose, It may be one or more selected from the group consisting of sodium pyrrolate and sodium sulfite.
• the activator may be added in an amount of 0.01 parts by weight to 2.0 parts by weight, 0.02 parts by weight to 1.5 parts by weight, or 0.05 parts by weight to 1.0 parts by weight based on 100 parts by weight of the total monomer mixture, and the polymerization rate within this range There is an effect that can maintain the appropriate level.
• the molecular weight control agent is, for example, ⁇ -methylstyrene dimer; mercaptans such as t-dodecyl mercaptan, n-dodecyl mercaptan, and octyl mercaptan; Halogenated hydrocarbons such as carbon tetrachloride, methylene chloride and methylene bromide; It may be one or two or more selected from the group consisting of sulfur-containing compounds such as tetraethyl thiuram disulfide, dipentamethylene thiuram disulfide and diisopropylxanthogen disulfide, and specific examples are mercaptans, and more As a specific example, it may be t-dodecylmercaptan.
• the molecular weight modifier may be added in an amount of 0.1 parts by weight to 2 parts by weight, 0.2 parts by weight to 1.5 parts by weight, or 0.3 parts by weight to 1.0 parts by weight based on 100 parts by weight of the total monomer mixture, and polymerization stability within this range This is excellent, and when manufacturing a molded article after polymerization, there is an effect of excellent physical properties of the molded article.
• the polymerization of the carboxylic acid-modified nitrile-based copolymer may be carried out in water as a medium, for example, deionized water, and in order to ensure ease of polymerization, a chelating agent, a dispersing agent, if necessary, Additives such as a pH adjuster, a deoxygenator, a particle size adjuster, an anti-aging agent and an oxygen scavenger may be further included.
• the emulsifier, polymerization initiator, molecular weight modifier, additive, etc. may be added in batches or dividedly into a polymerization reactor like the monomer mixture, and may be continuously added at each input.
• the polymerization of the carboxylic acid-modified nitrile-based copolymer may be carried out at a polymerization temperature of 10°C to 90°C, 20°C to 80°C, or 25°C to 75°C. There is an excellent effect of latex stability within the range.
• the method for preparing the carboxylic acid-modified nitrile-based copolymer latex may include the step of terminating the polymerization reaction to obtain a carboxylic acid-modified nitrile-based copolymer latex. Termination of the polymerization reaction of the carboxylic acid-modified nitrile-based copolymer may be carried out at a point where the polymerization conversion rate is 90% or more, 91% or more, or 92% to 99.9%, and the addition of a polymerization terminator, a pH adjuster, and an antioxidant. Can be carried out by In addition, the method for preparing the carboxylic acid-modified nitrile-based copolymer latex may further include a step of removing unreacted monomers by a deodorizing concentration process after the reaction is completed.
• the step of adding and mixing a cholate-based emulsifier to the prepared carboxylic acid-modified nitrile-based copolymer latex is, from the carboxylic acid-modified nitrile-based copolymer latex, dip molding for dip molding. It may be a step for preparing a latex composition for use.
• the type and content of the cholate-based emulsifier may be the same as described above.
• the cholate-based emulsifier may be different from the emulsifier introduced during polymerization described above.
• the cholate-based emulsifier is mixed with the prepared carboxylic acid-modified nitrile-based copolymer latex, thereby increasing the synergy time and improving tensile strength and stress (modulus).
• a molded article comprising a layer derived from the latex composition for dip molding.
• the molded article may be a dip molded article prepared by dip molding the latex composition for dip molding, and may be a molded article including a layer derived from the dip molding latex composition formed from the latex composition for dip molding by dip molding.
• the molded article manufacturing method for molding the molded article may include immersing the latex composition for dip molding by a direct immersion method, an anode adhesion immersion method, a Teague adhesion immersion method, etc. It can be carried out by an adhesion immersion method, and in this case, there is an advantage in that a dip-molded article having a uniform thickness can be obtained.
• the method of manufacturing a molded article may include the steps of attaching a coagulant to a dip mold (S100); Immersing the latex composition for dip molding in the dip molding mold to which the coagulant is attached to form a layer derived from the latex composition for dip molding, that is, a dip molding layer (S200); And heating the dip molding layer to crosslink the latex composition for dip molding (S300).
• the step (S100) is a step of attaching a coagulant to the surface of the dip molding mold by immersing the dip molding mold in a coagulant solution to form a coagulant in the dip molding mold, and the coagulant solution is a coagulant in water, alcohol, or a mixture thereof.
• the content of the coagulant in the coagulant solution may be 5% to 50% by weight, 7% to 45% by weight, or 10% to 40% by weight based on the total content of the coagulant solution.
• the coagulant may be, for example, a metal halide such as barium chloride, calcium chloride, magnesium chloride, zinc chloride, and aluminum chloride; Nitrates such as barium nitrate, calcium nitrate and zinc nitrate; Acetates such as barium acetate, calcium acetate, and zinc acetate; And it may be one or more selected from the group consisting of sulfates such as calcium sulfate, magnesium sulfate, and aluminum sulfate, and a specific example may be calcium chloride or calcium nitrate.
• a metal halide such as barium chloride, calcium chloride, magnesium chloride, zinc chloride, and aluminum chloride
• Nitrates such as barium nitrate, calcium nitrate and zinc nitrate
• Acetates such as barium acetate, calcium acetate, and zinc acetate
• sulfates such as calcium sulfate, magnesium sulfate, and aluminum s
• the step (S200) may be a step of immersing a dip molding mold to which a coagulant is attached to form a dip molding layer in the latex composition for dip molding according to the present invention, and taking it out to form a dip molding layer on the dip molding mold.
• step (S300) may be a step of crosslinking the latex composition for dip molding by heating a dip molding layer formed on a dip molding mold to obtain a dip molding product to perform curing.
• the crosslinked dip molding layer may be peeled off from the dip molding mold by heat treatment to obtain a dip molded article.
• the molded article may be a glove such as a surgical glove, an examination glove, an industrial glove and a household glove, a condom, a catheter, or a health care product.
• Thermometer, cooler, nitrogen gas inlet, and a 10L high-pressure reactor equipped to continuously inject monomers, emulsifiers, and polymerization initiators into the reactor with nitrogen, and then 30% by weight of acrylonitrile and 65 of 1,3-butadiene in the reactor.
• 100 parts by weight of a monomer mixture consisting of 5% by weight and 5% by weight of methacrylic acid, 2.5 parts by weight of sodium alkylbenzene sulfonate, 0.5 parts by weight of t-dodecyl mercaptan, and 140 parts by weight of ion-exchanged water were added, and the temperature was raised to 38°C.
• a coagulant solution was prepared by mixing 15 parts by weight of calcium nitrate, 84.5 parts by weight of distilled water, and 0.5 parts by weight of a wetting agent (Teric 320, Huntsman Corporation, Australia).
• the hand-shaped ceramic mold was immersed in the prepared coagulant solution for 1 minute, taken out, and dried at 80° C. for 4 minutes to apply the coagulant to the hand-shaped mold.
• the mold coated with the coagulant was immersed in the obtained latex composition for dip molding for 1 minute, taken out, and dried at 80° C. for 3 minutes. Subsequently, leaching was performed by soaking in water for 3 minutes, and the mold was dried at 80° C. for 3 minutes, and then crosslinked at 130° C. for 20 minutes. The crosslinked dip molded layer was peeled off from the hand-shaped mold to obtain a glove-shaped dip molded article.
• Example 1 when preparing the latex composition for dip molding, it was carried out in the same manner as in Example 1, except that 0.5 parts by weight of sodium cholate was added instead of 0.1 parts by weight.
• Example 1 the preparation of the latex composition for dip molding was carried out in the same manner as in Example 1, except that 1.0 part by weight of sodium cholate was added instead of 0.1 part by weight.
• Example 1 when preparing the latex composition for dip molding, it was carried out in the same manner as in Example 1, except that 3.0 parts by weight of sodium cholate was added instead of 0.1 parts by weight.
• Example 3 when preparing the latex composition for dip molding, except that 1.0 part by weight of sodium chenodeoxycholate (manufactured by Sigma-Aldrich, sodium chenodeoxycholate) was added as a cholate-based emulsifier instead of 1.0 part by weight of sodium cholate. It was carried out in the same manner as in Example 3.
• sodium chenodeoxycholate manufactured by Sigma-Aldrich, sodium chenodeoxycholate
• Example 1 when preparing the latex composition for dip molding, sodium cholate was not used, and it was carried out in the same manner as in Example 1.
• Example 1 the preparation of the latex composition for dip molding was carried out in the same manner as in Example 1, except that 0.01 parts by weight of sodium cholate was added instead of 0.1 parts by weight.
• Example 1 when preparing the latex composition for dip molding, it was carried out in the same manner as in Example 1, except that 0.05 parts by weight of sodium cholate was added instead of 0.1 parts by weight.
• Example 1 the preparation of the latex composition for dip molding was carried out in the same manner as in Example 1, except that 5 parts by weight of sodium cholate was added instead of 0.1 parts by weight.
• Example 3 when preparing the latex composition for dip molding, It was carried out in the same manner as in Example 3, except that 1.0 part by weight of sodium dodecyl sulfate (sodium dodecylsulfate, manufactured by Sigma-Aldrich) was added instead of 1.0 part by weight of sodium cholate.
• sodium dodecyl sulfate sodium dodecylsulfate, manufactured by Sigma-Aldrich
• Example 3 when preparing the latex composition for dip molding, It was carried out in the same manner as in Example 3, except that 1.0 part by weight of sodium dodecylbenzene sulfonate (manufactured by Sigma-Aldrich, sodium dodecylbenzene sulfonate) was added instead of 1.0 part by weight of sodium cholate.
• sodium dodecylbenzene sulfonate manufactured by Sigma-Aldrich, sodium dodecylbenzene sulfonate

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